ABSTRACT
Thermoplastic polymers are a compelling class of materials for emerging space exploration applications due to their wide range of mechanical properties and compatibility with a variety of processing methods, including additive manufacturing. However, despite these benefits, the use of thermoplastic polymers in a set of critical space applications is limited by their low electrical conductivity, which makes them susceptible to static charging and limits their ability to be used as active and passive components in electronic devices, including materials for static charge dissipation, resistive heaters, and electrodynamic dust shielding devices. Herein, we explore the microstructural evolution of electrically conductive, surface-localized nanocomposites (SLNCs) of chemically modified reduced graphene oxide and a set of thermoplastic polymers as a function of critical thermal properties of the substrate (melting temperature for semi-crystalline materials or glass transition temperature for amorphous materials). Selected offsets from critical substrate temperatures were used to produce SLNCs with conductivities between 0.6-3 S/cm and surface structures, which ranged from particle-rich, porous surfaces to polymer-rich, non-porous surfaces. We then demonstrate the physical durability of these electrically conductive SLNCs to expected stress conditions for flexible conductive materials in lunar applications including tension, flexion, and abrasion with lunar simulant. Small changes in resistance (R/R0 < 2) were measured under uniaxial tension up to 20% strain in high density polyethylene and up to 500 abrasion cycles in polysulfone, demonstrating the applicability of these materials as active and passive flexible conductors in exterior lunar applications. The tough, electrically conductive SLNCs developed here could greatly expand the use of polymeric materials in space applications, including lunar exploration, micro- and nano-satellites, and other orbital structures.
ABSTRACT
Understanding and manipulating the miscibility of donor and acceptor components in the active layer morphology is important to optimize the longevity of organic photovoltaic devices and control power conversion efficiency. In pursuit of this goal, a "porphyrin-capped" poly(3-hexylthiophene) was synthesized to take advantage of strong porphyrin:fullerene intermolecular interactions that modify fullerene miscibility in the active layer. End-functionalized poly(3-hexylthiophene) was synthesized via catalyst transfer polymerization and subsequently functionalized with a porphyrin moiety via post-polymerization modification. UV-vis spectroscopy and X-ray diffraction measurements show that the porphyrin-functionalized poly(3-hexylthiophene) exhibits increased intermolecular interactions with phenyl-C61-butyric acid methyl ester (PCBM) in the solid state compared to unfunctionalized poly(3-hexylthiophene) without sacrificing microstructure ordering that facilitates optimal charge transport properties. Additionally, differential scanning calorimetry revealed porphyrin-functionalized poly(3-hexylthiophene) crystallization decreased only slightly (1-6%) compared to unfunctionalized poly(3-hexylthiophenes) while increasing fullerene miscibility by 55%. Preliminary organic photovoltaic device results indicate device power conversion efficiency is sensitive to additive loading levels, as evident by a slight increase in power conversion efficiency at low additive loading levels but a continuous decrease with increased loading levels. While the increased fullerene miscibility is not balanced with significant increases in power conversion efficiency, this approach suggests that integrating non-bonded interaction potentials is a useful pathway for manipulating the morphology of the bulk heterojunction thin film, and porphyrin-functionalized poly(3-hexylthiophenes) may be useful additives in that regard.
ABSTRACT
Despite tremendous progress in using additives to enhance the power conversion efficiency of organic photovoltaic devices, significant challenges remain in controlling the microstructure of the active layer, such as at internal donor-acceptor interfaces. Here, we demonstrate that the addition of low molecular weight poly(3-hexylthiophene)s (low-MW P3HT) to the P3HT/fullerene active layer increases device performance up to 36% over an unmodified control device. Low MW P3HT chains ranging in size from 1.6 to 8.0 kg/mol are blended with 77.5 kg/mol P3HT chains and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) fullerenes while keeping P3HT/PCBM ratio constant. Optimal photovoltaic device performance increases are obtained for each additive when incorporated into the bulk heterojunction blend at loading levels that are dependent upon additive MW. Small-angle X-ray scattering and energy-filtered transmission electron microscopy imaging reveal that domain sizes are approximately invariant at low loading levels of the low-MW P3HT additive, and wide-angle X-ray scattering suggests that P3HT crystallinity is unaffected by these additives. These results suggest that oligomeric P3HTs compatibilize donor-acceptor interfaces at low loading levels but coarsen domain structures at higher loading levels and they are consistent with recent simulations results. Although results are specific to the P3HT/PCBM system, the notion that low molecular weight additives can enhance photovoltaic device performance generally provides a new opportunity for improving device performance and operating lifetimes.
